Decorative paint film laminate

ABSTRACT

A decorative paint film laminate having high gloss and distinctness of image after processing for providing a decorative finish for a part, the decorative paint film laminate comprises a paint film having an inner surface and an outer surface, a backing sheet applied to the inner surface of the paint film, and no mask on the outer surface of the paint film. The paint film comprises a clear coat layer, a gloss and distinctness of image retaining layer, and a color coat layer. The paint film obtains high gloss and distinctness of image without a mask being on the outer surface of the paint film.

FIELD OF THE INVENTION

The present invention relates to a decorative paint film laminate thathas high gloss and distinctness of image after processing without theuse of a mask on the outer surface of the paint film, and a method forthe making of the decorative paint film laminate.

BACKGROUND OF THE INVENTION

Manufacturers have shown increasing interest in using paint film in lieuof spray painting for providing a decorative surface finish for partssuch as automotive body parts. These parts can be manufactured using oneor more of the following forming or molding processes: thermoforming,injection molding, or compression molding. In general, most processesusing paint film such as thermoforming involve forming the film into athree dimensional shape and involve the use of heat and pressure.Depending upon a variety of factors including, for example, the geometryof an automobile body part, the automobile body part may or may notrequire an injection molding process, as long as the part is sturdyenough to facilitate the manufacturing process and is suitable for theintended end use application.

Paint films have been used for many years in a variety of applicationsand uses. Current products tend to lose gloss and distinctness of image(DOI) when processed, such as thermoformed, especially in high stretchareas. In many of the current paint film applications, especially highstretch applications, this deficiency has been overcome with the use ofa mask to achieve high gloss and DOI for the surface finishes duringthermoforming. In order to maintain the gloss and DOI, the mask musthave sufficient modulus at the thermoforming temperature to maintain thesmooth surface finish. In these applications, a thermoformable mask filmis applied and removably adhered to the clear coat surface of thedecorative sheet before the thermoforming process. In many cases, themask is removed and discarded during the part manufacturing process, forexample, before the injection molding process. The materials andmanufacturing process of the mask film add significant cost to the partsproduced using paint film. In addition, the use of the mask, in somecases, complicates the forming and molding processes. For example, themask may need to be removed before an injection molding process toprevent the difficulty of removal after the parts are molded. The maskmay be difficult to remove because it has been stretched substantiallyand becomes prone to tear and must be removed in pieces addingsignificant labor and possible contamination in subsequent processing.Furthermore, to date, known masked paint films have not been able toachieve a 20° gloss that is within the lower gloss range of traditionalpaints. Therefore, the present invention attempts to address and solvethese problems.

SUMMARY OF THE INVENTION

The present invention relates to a decorative paint film laminate havingimproved high gloss and distinctness of image (DOI) after processingwithout the use of a mask on the outer surface of the paint film. Thedecorative paint film laminate basically comprises a gloss and DOIretaining layer in addition to a clear coat layer and a color coatlayer. The gloss and DOI retaining layer functions an “internal” maskand has, among other properties, excellent clarity, good adhesion toboth clear and color layers, good weatherability, and thermoformability.

The decorative paint film laminate comprises a paint film having aninner surface and an outer surface, and a backing sheet applied to theinner surface of the paint film. The paint film comprises a clear coatlayer, a gloss and DOI retaining layer, and a color coat layer. Thepaint film may optionally comprise any of a color adjustment layer, aprimer layer, and an adhesive layer. Also within the scope of thepresent invention is a composite shaped part, a method of making adecorative paint film laminate, and a paint film comprising a gloss andDOI retaining layer.

Further areas of applicability of the present invention will becomeapparent from the detailed description provided hereinafter. It shouldbe understood that the detailed description and specific examples, whileindicating the preferred embodiment of the invention, are intended forpurposes of illustration only and are not intended to limit the scope ofthe invention.

BRIEF DESCRIPTION OF THE DRAWINGS

The present invention will become more fully understood from thedetailed description and the accompanying drawings, wherein:

FIG. 1 is a perspective view of an automobile illustrating the frontfascia of an automobile having a decorative paint film applied thereto;

FIG. 2 is a front view of an automobile front fascia having a decorativepaint film applied thereto;

FIG. 3 is a cross-sectional view of the fascia shown in FIG. 2 takenalong line 3-3 of FIG. 2;

FIG. 4 is a cross-sectional view of the decorative paint film laminateof the present invention adhered to a substrate;

FIG. 5 is a cross-sectional view of the decorative paint film laminateof the present invention including a clear coat layer, gloss and DOIretaining layer, a color adjustment layer, and a color coat layer;

FIG. 6 is a schematic illustration of a process for construction of thedecorative paint film laminate in accordance with the present invention;

FIGS. 7A-7D are schematic illustrations of the steps in a thermoformingprocess used to construct a preform; and

FIGS. 8A-8C are schematic illustrations of steps in an injection moldingprocess for forming a composite shaped part.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

The present invention will now be described more fully hereinafter withreference to the accompanying drawings. The following description of thepreferred embodiment(s) is merely exemplary in nature and is in no wayintended to limit the invention, its application, or uses.

The decorative paint film laminate of the present invention eliminatesthe need for a mask on the outer surface of a paint film in order tomake a part, such as an automobile part, having high gloss anddistinctness of image (DOI) using paint film technology. The term“mask”, as defined herein, refers to any material that is adhered to,removably or otherwise, to the outer surface of a paint film.Elimination of the need for a mask on the outer surface of a paint filmsimplifies the manufacturing process during forming and moldingprocesses and also reduces the cost of materials for making a part.

Referring now to the accompanying drawings and initially to FIG. 1, thedecorative paint film laminate of the present invention is indicated inFIG. 1 by reference numeral 14 and basically comprises a clear coatlayer, a gloss and DOI retaining layer, a color coat layer, an optionalprimer layer, an optional adhesive layer, and a backing sheet.

FIG. 1 illustrates an automobile 10 having a composite shaped part 12.As shown, the composite shaped part 12 is a complex, contouredthree-dimensional front fascia of the automobile 10. The compositeshaped part 12 has a decorative paint film laminate 14 applied thereto.Although not limited to such applications, the decorative paint filmlaminate 14 of the present invention is particularly advantageous forproviding a decorative surface on a composite shaped part 12 of anautomobile 10. However, those skilled in the art will appreciate thatthe present invention could be used in a variety of applicationsrequiring a decorative surface having high gloss and DOI.

FIG. 2 is a front view of the composite shaped part 12 having thedecorative paint film laminate 14 applied thereto. FIG. 3 is across-sectional side view of the composite shaped part 12 comprising asubstrate 16 having a decorative paint film laminate 14 applied thereto.As illustrated in FIG. 3, the decorative paint film laminate 14undergoes different amounts of elongation at different points along thecontoured surface of the composite shaped part 12. In one embodiment,the decorative paint film laminate 14 of the present invention has athree-dimensional configuration in which certain areas of the paint filmlaminate have been subjected to elongation up to, and even in excess of,about 300%, and other areas of the paint film laminate are substantiallynon-elongated. The decorative paint film laminate 14 of the presentinvention is capable of maintaining not only a uniform level of glossbut also a high level of gloss, regardless of the amount of elongationexperienced by the decorative paint film laminate 14 during a forming ormolding process.

FIG. 4 shows a greatly expanded cross-sectional view of a compositeshaped part 12 comprising a decorative paint film laminate 14 of thepresent invention adhered to a substrate 16. The decorative paint filmlaminate 14 includes a clear coat layer 22, a gloss and DOI retaininglayer 23, a color coat layer 24, an optional primer layer 26, anoptional adhesive layer 28, and a backing sheet 30.

The decorative paint film laminate 14 of the present invention not onlyretains both high gloss and DOI during forming and molding processes inthe absence of a mask on the outer surface of the paint film but alsoimproves the gloss and DOI of the paint film due to the presence of thegloss and DOI retaining layer. Examples of forming processes include,but are not limited to, thermoforming, cold stretching, and vacuumforming. Examples of molding processes include, but are not limited to,injection molding, compression molding, and blow molding.

Current commercial paint film products utilize a removable,thermoformable mask to minimize the gloss and DOI reduction during thethermoforming or molding processes. In those situations, the mask layeris the outer layer of the decorative paint film laminate. The clear coatlayer 22 in the present invention is the outer layer of the decorativepaint film laminate 14 during construction of the final product, such asan automobile. Therefore, a benefit of the decorative paint filmlaminate of the present invention is enhanced gloss and DOI of the paintfilm despite the absence of a mask layer on the outer surface of thepaint film. Thus, the present invention, is advantageous not onlybecause no mask is needed, but also because the gloss and DOI of thepaint film are enhanced with the presence of the gloss and DOI retaininglayer as compared to a paint film with a mask but no gloss and DOIretaining layer. Furthermore, there are no material, manufacturing,labor or other costs incurred due to the presence and ultimate removalof a mask from the clear coat layer. When a mask is used, the mask layermust be releasably bonded to the underlying decorative paint film andmust be stripped away from the underlying layers in a single piece. Thedecorative paint film laminate of the present invention eliminates theneed for a mask.

The weatherable outer surface of a standard paint film has an initial 20and 60 degree gloss of at least about “60” in dry film form. Afterthermoforming the dry film laminate, the 20 degree gloss and 60 degreegloss may decline by 50% or more in high stretch applications. Adheringa mask layer to the paint film may improve the 20 degree and 60 degreegloss retention but still shows gloss loss during the forming process,especially the 20 degree gloss. Industry standards typically requirethat the 20 degree gloss and 60 degree gloss be above 60 for manyapplications. However, the desired final gloss value, of the paint filmwill vary depending on the application. In contrast, the decorativepaint film laminate of the present invention has enhanced high gloss andDOI as compared to a standard paint film laminate with a mask.

FIG. 4 and FIG. 5 are greatly expanded cross-sectional views of thedecorative paint film laminate 14 of the present invention. As shown inFIGS. 4 and 5, the decorative paint film 18 may comprise a clear coatlayer 22, a gloss and DOI retaining layer 23, an optional coloradjustment layer 27 (shown in FIG. 5), and a color coat layer 24. Theclear coat layer 22 is formed from a substantially transparentweatherable, UV protective polymer composition selected to provide afilm which will not significantly fade, peel, crack, or chalk whenexposed to the environment for the intended life of the part 12 orfulfill other characteristics desired such as toughness, scratchresistance, and marr resistance, for example. Additionally, the clearcoat layer 22 must be formable from a two-dimensional surface to athree-dimensional surface without objectionable loss of appearance orperformance properties. The clear coat layer 22 may include, but is notlimited to: urethane polymers such as. polyurethane; acrylic polymers;fluoropolymers such as polyvinyl fluoride (PVF) and polyvinylidenefluoride (PVDF); and alloys of a fluoropolymer and an acrylic polymer.TEDLAR® manufactured by. DuPont of Wilmington, Del. is an example of apolyvinyl fluoride. FLUOREX® films manufactured by Soliant, LLC ofLancaster, S.C. are examples of alloys of a fluoropolymer and an acrylicpolymer such as a PVDF/acrylic alloy. The clear coat layer 22 mayinclude other additives including, but not limited to, UV screeners,antioxidants, heat stabilizers, and other conventional additives.Preferably, the clear coat layer 22 is about 0.3 mils to about 3 mils inthickness, more preferably from about 0.5 mils to about 2.5 mils inthickness. Preferably, the clear coat layer is applied in the form of asolution.

In one embodiment, the outermost layer of the paint film 18, such as theclear coat layer 22, comprises an alloy of a fluoropolymer and anacrylic polymer. For example, the alloy of fluoropolymer and acrylicpolymer may comprise about 30 to about 70 weight percent fluoropolymer,and about 30 to about 70 weight percent acrylic polymer on a dry solidsbasis. A commercially available fluoropolymer is KYNAR SL manufacturedby Arkema, Inc. of Philadelphia, Pa. Commercially available acrylicpolymers are Elvacite 2041 manufactured by INEOS Acrylics of Cordova,Tenn. and Acryloid A11 manufactured by Rohm & Haas of Philadelphia, Pa.

The gloss and DOI retaining layer 23 serves as an “internal mask” suchthat the decorative paint film laminate 14 has improved high gloss andDOI as compared to the use of a mask on the outer surface of a paintfilm. The composition of the gloss and DOI retaining layer 23 ispreferably selected such that the tensile strength of the gloss and DOIretaining layer is the same as or higher than the higher of the tensilestrength of either the clear coat layer or the color coat layer at thethermoforming temperature. More preferably, the gloss and DOI retaininglayer has a tensile strength that is higher than the higher of thetensile strength of either the clear coat layer or the color coat layerat the thermoforming temperature. The thermoforming temperature variesdepending upon the composition of the materials selected for use in thelayers. However, the thermoforming temperature would be known to one ofordinary skill in the art for a given material. The term “thermoformingtemperature”, as used herein, refers to the temperature at which athermoplastic material is shaped or formed. Therefore, materialssuitable for use in the gloss and DOI retaining layer may include, butare not limited to, urethanes, acrylics, fluoropolymers, nylons, alloysor combinations thereof. An example of a preferred urethane includes,but is not limited to, polyurethane. Examples of preferredfluoropolymers include, but are not limited to, polyvinylidene fluoride(PVDF), polyvinyl fluoride (PVF) and alloys or combinations thereof.TEDLAR® is an example of a polyvinyl fluoride manufactured by DuPont ofWilmington, Del.

The gloss and DOI retaining layer may be applied, for example, in theform of a dispersion or a solution. The gloss and DOI retaining layer ispreferably cast or coated. The gloss and DOI retaining layer ispreferably about 0.2 mils to about 2.0 mils in thickness.

A cross-linking agent may be used in the gloss and DOI retaining layer.Examples of cross-linking agents include, but are not limited to,poly-aziridine, poly-isocyanate, blocked poly-isocyanate, and aminocross-linking agents. XAMA 7 is an example of a commercially availablepoly-aziridine cross-linking agent manufactured by Bayer Corp. ofPittsburgh, Pa. API—972 is an example of a commercially availableblocked isocyanate manufactured by Advanced Polymer, Inc. of Carlstadt,N.J. The level of cross-linking agent may vary from 0.1 to 4.0 percentof the solids of the formulation.

Commercially available examples of polyurethane polymers may include,cross-linkable polyurethane dispersions such as HYBRIDUR 580 andHYBRIDUR 870, both manufactured by Air Products of Allentown, Pa.; HD4669 and HD 2113, both manufactured by C.L. Hauthaway and SonsCorporation of Lynn, Mass.

Commercially available examples of acrylic polymers used for solventcasting may include, but are not limited to, ELVACITE 2041, ELVACITE2014 and ELVACITE 2552, all of which are manufactured by INEOS Acrylicsof Cordova, Tenn.; and Br85, manufactured by Dianal America, Inc. ofPasadena, Tex.

Commercially available acrylic dispersions suitable for use in thisinvention include, but are not limited to, AS 2505 and AS 2511, bothmanufactured by Alberdingk Boley, Inc. of Charlotte, N.C.

The color coat layer 24 is formed of a polymer composition comprising auniformly dispersed pigment and/or metallic flakes or pearlescents toprovide the appearance necessary for exterior automobile use.Preferably, the color coat layer 24 may comprise a polymer selected fromthe group consisting of urethanes such as polyurethane, acrylics,fluoropolymers such as PVDF, and alloys and combinations thereof.FLUOREX® films manufactured by Soliant, LLC of Lancaster, S.C. areexamples of alloys of a fluoropolymer and an acrylic polymer. The colorcoat layer 24 may include pigments, dyes, and/or flakes to enhancevisual appearance and improve weatherability. Preferably, the color coatlayer 24 is about 0.2 to about 3 mils in thickness, more preferably 0.2mils to 2.5 mils in thickness.

If desired, a color adjustment layer 27 may be added between the clearcoat layer 22 and the color coat layer 24 to enhance visual appearance,preferably between the gloss and DOI retaining layer and the color coatlayer. The color adjustment layer 27 can be applied in coating form andmay include pigments, dyes and/or flakes or applied as a graphic designusing printing methods such as gravure, rotary screen, flat bedstep-and-repeat screen, ink jet, flexographic or other printingtechniques. This layer is typically used for appearance purposes tomatch three layer paint systems.

The primer layer 26 is an optional layer that improves adhesion betweenthe color coat layer 24 and the adhesive layer 28. The primer layer 26preferably comprises an acrylic polymer prepared in solution using anycompatible solvent known in the art, such as toluene. In one embodiment,the primer layer 26 is prepared from a solution comprising about 50 toabout 85 weight percent acrylic composition and about 5 to about 20weight percent solvent. An acrylic polymer suitable for use in theprimer layer 26 is acrylic adhesive 68070 manufactured by DuPont. Theprimer layer 26 may be opaque, colored or clear. Opaque is defined asless than 1 percent transmission at a wavelength of less than 400 nm.The primer layer 26 is preferably about 0.2 to about 2 mils inthickness. The primer layer 26 may be colored or opaque to protect theunderlying backing sheet 30 from damage caused by UV exposure. Pigments,such as carbon black, titanium oxide, and mixtures thereof, may be addedto impart color to the acrylic polymer composition used in the primerlayer 26. Additionally, additives such as UV screeners, antioxidants,and heat stabilizers may be added to the primer layer 26.

An optional adhesive layer 28 may be used to adhere the decorative paintfilm 18 to a backing sheet 30. The composition of the adhesive dependsupon, among other factors, the chemistry of color layer and the type ofbacking sheet used. For certain substrates such as ABS and polystyrenesubstrates, the presence of the adhesive layer is often not preferred.However, for other backing sheets such as thermoplastic polyolefin(TPO), an adhesive layer may be preferred. An example of a suitableadhesive for TPO is an acrylic primer/CPO adhesive.

The adhesive layer 28 may include, but is not limited to, one or morelayers of urethane adhesives, acrylic adhesives, acrylic adhesives withcross linkers, chlorinated polyolefins and mixtures thereof. Preferably,a mixture of a chlorinated polypropylene and a higher molecular weightchlorinated polyolefin is used. In one embodiment, the adhesive layer 28is prepared from a mixture of about 5 to about 20 weight percentchlorinated polypropylene and about 1 to about 10 weight percent of ahigher molecular weight chlorinated polypropylene formed in solution. Acompatible solvent known in the art, such as toluene, is present in anamount of about 60 to about 80 weight percent. A chlorinatedpolypropylene suitable for use with the present invention is HARDLEN 13LP manufactured by Advanced Polymer. A higher molecular weightchlorinated polyolefin suitable for use with the present invention isSUPERCHLON 822S manufactured by CP/Phibrochem of Fort Lee, N.J. Theadhesive layer 28 should preferably be capable of stretching about 20 toabout 600 percent.

Due to the substantial elongation capability of the adhesive layer 28,the adhesive layer maintains the necessary adhesive strength to preventdelamination of the decorative paint film 18 from the backing sheet 30over a wide temperature range.

An epoxy component, such as EPON 828RS manufactured by Shell Chemical,may be added in small amounts (approximately about 0.1 to about 2.0weight percent on a dry solids basis) as an acid scavenger. As with theprimer layer 26, the adhesive layer 28 may be colored or opaque toprotect the underlying thermoformable backing sheet 30 from damagecaused by UV exposure. Pigments, such as carbon black, titanium oxide,and mixtures thereof, may be added to impart color to the polymercomposition used in the adhesive layer 28. Additives including, but notlimited to, UV screeners, antioxidants, and heat stabilizers may beadded to the adhesive layer 28. Preferably, the adhesive layer 28 isabout 0.2 to about 2 mils in thickness.

The backing sheet 30 bonds the decorative paint film 18 of thedecorative paint film laminate 14 to the substrate 16. In addition, thebacking sheet 30 provides bulk and/or rigidity for handling thedecorative paint film laminate 14 as a thermoformed preform. The backingsheet 30 also provides thickness to prevent glass fibers, fillers orother sources of visual roughening or “orange peel” from the substrate16 from affecting the visual appearance of the decorative paint filmlaminate 14. The backing sheet 30 must bond well with both the substrate16 and the adhesive layer 28. The backing sheet 30 may be of a materialincluding, but not limited to, thermoplastic polyolefin,acrylonitrile-butadiene-styrene (ABS) terpolymer, polypropylene,polyethylene, thermoplastic polyimide, polyethylene oxide,polycarbonate, polyvinyl chloride, polystyrene, styrene/polyphenyleneoxide (NORYEL), polybutylene terephthalate, nylon, PETG copolyester, andmixtures, laminates, copolymers and other combinations thereof,depending on the material used as the substrate 16.

FIG. 6 illustrates a process for constructing the decorative paint filmlaminate 14 of the present invention: As, shown, a film carrier 33 isadvanced from a supply roll 38 through a series of process steps. Thefilm carrier 33 preferably comprises a polyester casting film having ahigh gloss surface. The film carrier 33 is important for high glossapplications because it imparts high gloss and DOI to the decorativepaint film laminate 14. Advantageously; the film carrier 33 comprisespolyethylene terephthalate (PET) in a grade without slip additives. Thefilm carrier 33 is about 1 to about 3 mils in thickness, preferablyabout 2 mils in thickness:

The film carrier 33 passes through a first coating station 40. If adecorative paint film 18 having multiple coatings is desired, the firstcoating station 40 may deposit the clear coat layer 22. The clear coatlayer 22 then passes through a dryer 41. Next, the gloss and DOIretaining layer is deposited and dried by dryer 43. Thereafter, a colorcoat layer 24 is deposited on the gloss and DOI retaining layer 23 usingcoating station 44. The color coat layer 24 is then dried using dryer46. Optionally, the dried color coat layer 24 can be subjected to acorona treatment (not shown).

The coating stations 40, 42, and 44 may utilize any conventional coatingor casting techniques, such as reverse roll coating or slot die coatingtechniques. Slot die coating methods are preferred. The dryers 41, 43,and 46 may utilize any conventional drying technique. Preferably, thedryers 41, 43, and 46 are ovens having multiple heating zones whereineach successive heating zone operates at a progressively highertemperature. For example, an oven having four to six heating zonesranging in temperature from about 200° F. to about 425° F. may be used.Alternatively, dryer 41 may be eliminated from the process such that thegloss and DOI retaining layer is applied to the clear coat 22 while theclear coat is still wet using a “wet on wet” coating technique.

After the decorative paint film 18 is applied to the film carrier 33,the film carrier advances to a primer coating station 48, where theprimer layer 26 is deposited onto the exposed layer of the decorativepaint film 18. The primer layer 26 is then dried using dryer 49.Thereafter, the film carrier advances to an adhesive coating station 50,where the adhesive layer 28 is deposited onto the primer layer 26.Thereafter, the adhesive layer 28 is dried using dryer 51. The primercoating station 48 and adhesive coating station 50 may utilize anyconventional coating or casting technique, such as reverse roll coatingor slot die coating techniques. The dryers 49 and 51 may utilize anyconventional drying technique. Alternatively, dryer 49 may be eliminatedfrom the process such that the adhesive layer 28 is applied to theprimer layer 26 while the primer layer is still wet using a “wet on wet”coating technique known by one of ordinary skill in the art.Alternatively, the CPO/Primer can be coated directly on PET in awet-on-wet process and then laminated using heat and pressure to thecolor layer of the paint film.

A backing sheet 30 is advanced from a supply roll 52 and laminated tothe adhesive-coated surface of the film carrier 31 Optionally, thebacking sheet 30 can be subjected to a corona treatment (not shown)prior to lamination. The resulting laminate is collected by product roll54.

The decorative paint film laminate 14 of the present invention can beadhered to a supporting substrate 16 in accordance with known laminatingor bonding techniques. Illustrative examples of supporting substrates 16include, but are not limited to, metal, wood, and molded polymersubstrates. As explained above, exterior automobile parts areparticularly suitable as the substrate 16. Suitable polymers for use asthe substrate 16 include, but are not limited to, thermoplastic olefin,acrylonitrile-butadiene-styrene terpolymer, polypropylene, thermoplasticpolyimide, polyethylene oxide, polycarbonate, polyvinyl chloride,polystyrene, styrene/polyphenylene oxide (NORYEL), polybutyleneterephthalate, nylon, PETG copolyester, Sheet Molding Compounds (SMC),RIM urethanes, mixtures, laminates, and copolymers thereof.

The decorative paint film laminate 14 may be applied to the substrate 16by a variety of methods. These methods include, but are not limited to,compression molding, such as thermoplastic or thermoset compressionmolding, injection molding and the like. In an injection moldingprocess, the decorative paint film laminate 14 may be preformed asdescribed below or placed in the mold as a substantially flat sheet. Ifthe paint film laminate 14 is placed in the mold without preforming, theheat and/or pressure of the molding process conforms the paint filmlaminate to the desired shape.

FIGS. 7A-7D illustrate the steps in a thermoforming process.Thermoforming is often used to create a preform in a three-dimensionalconfiguration that roughly approximates the three-dimensionalconfiguration of the final product. However, other forming processesknown in the art may be used. The preform is then placed in a mold forin-mold surfacing of a desired substrate 16 to form the final product.FIG. 7A shows heating of the decorative paint film laminate 14 of thepresent invention by heating elements 70. The heating step softens andincreases the extensibility of the decorative paint film laminate 14 sothat the paint film laminate will readily conform to the contoured outersurface of the mold 74. As shown in FIG. 7C, the mold 74 is brought intocontact with the heated decorative paint film laminate 14 and a vacuumis drawn to encourage conformity of the paint film laminate 14 to thecontours of the mold 74. Thereafter, the mold 74 is removed from thedecorative paint film laminate 14 and the paint film laminate is allowedto cool and harden into the three-dimensional configuration.

FIGS. 8A-8C illustrate steps in an in-mold surfacing process. As shownin FIG. 8A, the thermoformed decorative paint film laminate 14 is placedin the mold cavity 78 of an injection mold 76. The decorative paint filmlaminate is placed in the mold cavity 78 with the clear coat layer 22facing the inner surface of the injection mold 76. Alternatively, thedecorative paint film laminate 14 may be placed in the mold cavity 78 asa flat, two-dimensional insert rather than as a preform. The injectionmold 76 is shut and a moldable polymer 82 is introduced into the mold 76through the injection mold barrel 80. The polymer 82 bonds to thebacking sheet 30 and conforms to the contoured shape of the mold cavity78. Thereafter, the moldable polymer 82 is allowed to cool and hardeninto a composite shaped part 12 comprising a substrate 16 bonded to adecorative paint film laminate 14, as shown in FIG. 8C.

EXAMPLES Example 1

Clear coat compositions were prepared in accordance with the presentinvention and are identified as Clear Coat Compositions A and B,respectively. The component amounts are based upon the total weight ofthe composition being on a 1 gram basis.

Clear Coat Composition A

TINUVIN 292 0.01184 g TINUVIN 928 0.01184 g ACRYLOID A11 0.15387 gELVACITE 2041 0.03957 g KYNAR SL 0.08288 g MEK 99.4% 0.59500 gCyclohexanone 0.10500 g

For the above formulation, TINUVIN 292 and TINUVIN 928 were added in theMEK/Cyclohexanone solvent blend first. The additives were stirred untildissolved. ACRYLOID A11, ELVACITE 2042 and KYNAR SL were added into themix and stirred with high shear until the resins were dissolved.

Clear Coat Composition B

KYNAR SL 0.09220 g TINUVIN 928 0.00946 g TINUVIN 292 0.00946 g ACRY68080 0.43480 g Ethyl Acetate 0.45404 g

For the above formulation the TINUVIN 292 and TINUVIN 928 were added inEthyl Acetate solvent first. The additives were stirred until dissolved.KYNAR SL was then added into the mix and stirred with high shear untilthe resins were dissolved. ACRY 68080 was then added into the mix slowlywith high shear.

Example 2

Gloss and DOI Retaining Compositions were prepared in accordance withthe present invention and are identified as Gloss and DOI RetainingCompositions A, B, C, and D, respectively. The component amounts arebased upon the total weight of the composition being on a 1 gram basis.

Gloss and DOI Retaining Composition A

HD 4669 0.3902 g HD 2113 0.5854 g API-792 0.0244 g

In Composition A, the HD4669 and HD2113 were mixed, and then thecross-linker API-792 was added and mixed for another 15 minutes.

Gloss and DOI Retaining Composition B

DPNB 0.12675 g HYBRIDUR 580 0.77773 g Deionized Water 0.08385 g XAMA-70.01167 g

Gloss and DOI Retaining Composition C

DPNB 0.12675 g HYBRIDUR 580 0.69996 g AS 2505 0.07777 g Deionized Water0.08385 g XAMA-7 0.01167 g

Compositions B and C were prepared as set forth below in Composition Dby preparing a Pre-Mix with Diproplene Glycol Butyl Ether (DPNB).

Gloss and DOI Retaining Composition D

Glycol Ether DPNB 0.11776 g SURFYNOL DF-58 0.00140 g BYK 346 0.00435 gINHB TINUVIN 0.00992 g BYK 333 0.00062 g HYBRIDUR 580 0.72329 gDeionized Water 0.13181 g CYMEL 385 0.01085 g

Gloss and DOI Retaining Composition D was prepared by first preparing aPre-Mix as follows. DPNB solvent commercially available from LyondellChemical Company of Houston, Tex. was weighed into anappropriately-sized, grounded container. While stirring vigorously withhigh shear, TINUVIN 384 commercially available from Ciba SpecialtyChemicals of Tarrytown, N.Y. was added to the container and measuredaccurately. Stirring was continued and BYK 346 commercially availablefrom BYK Chemie of Germany was added. The container was rinsed with mix,and the rinse was added. Stirring was continued, and BYK 333commercially available from BYK Chemie of Germany was added. Thecontainer was rinsed with mix, and the rinse was added. Stirring wascontinued, and SURFYNOL DF-58 commercially available from Air Productand Chemicals of Allentown, Pa. was added. The container was rinsed withmix, and the rinse was added. The Pre-Mix was stirred for a minimum of15 minutes or until all components were completely dissolved.

After preparation of the Pre-Mix, HYBRIDUR 580 commercially availablefrom by Air Products of Allentown, Pa. was weighed out. Using a highshear mixer with an appropriately sized F-style Cowles blade (Vat-use16″ blade, Drum-use 8″ blade), stirring was begun with a good vortex(˜700 RPM). While stirring, the specified amount of the DPNB Pre-Mix wasslowly poured. The DPNB caused the viscosity to rise, so the mixer speedwas increased when adding the Pre-Mix, as necessary. One-third of thespecified amount of deionized water was added. The vat was tightlycovered with clear polyethylene film, and the mixture was stirred untilthe temperature reached 85° F. The time until temperature was reachedwas recorded. CYMEL 385 commercially available from Cytec IndustriesInc. of West Paterson, N.J. was added and stirring was continued. Theremaining two-thirds of the deionized water was added and stirred forthirty additional minutes. The vat was kept covered with polyethylenefilm. The mix temperature was monitored closely and was not allowed toexceed 85° F. The completed mix required a minimum sit time of 72 hoursprior to coating.

Example 3

The following color coat compositions were prepared by starting with aclear base. An example of the clear base for the color coat is set forthbelow.

Clear Base for the Base Coat

ELVACITE 2042 0.24000 g MEK 99.4% 0.42000 g XYLENE 0.17165 g TINUVIN 1230.00278 g TINUVIN 900 0.00557 g ELVACITE R4402 0.16000 g

Black Color Formulation

ACRY BLK B14276-M139 0.10666 g ACRY WH W14276 M70 0.00444 g ACRYLICCLEAR BASE 0.88890 g

White Color Formulation

ACRY WH W14276 M70 0.19977 g ACRY 29Y1038 TRANS YELL 0.00111 g ACRYLICCLEAR BASE 0.79912 g

D4D Acrylic Glossy Silver

ACRYLIC CLEAR BASE 0.90400 g ALUM PASTE 3201 0.08000 g DISP ACRY WHW14276 M70 0.01200 g ACRY BLK B14276-M139 0.00400 g

Example 4

Example 4 is illustrative of the preparation of a decorative paint filmlaminate and the thermoforming process.

The paint film samples (clear coat/color coat or clear coat/glossretaining layer/color coat) were made from a production machine ofSoliant, LLC of Lancaster, S.C. TPO adhesive was also coated onto thepaint film on the production machine. The laminate samples were preparedby laminating the paint film with TPO adhesive to 30 mil TPO substratesusing a lab laminator manufactured by Talboys Engineering Company ofEmerson, N.J. with the hop nip temperature of 360° F. The laminationspeed used was about 10 ft/min. The laminates were then thermoformedover a wood body side mold (Toyoto, 770 N body side mold) at 330° F.using a thermoformer manufactured by ZMD International, Inc, Model HD333. Ninety percent (90%) of the maximum heat output was used for bothtop and bottom heat. The temperature was measured by an IR gun and fromthe substrate surface.

Gloss and DOI were recorded before and after thermoforming. The glosswas measured by the Micro-Tri-Gloss meter manufactured by BYK. Gardnerlocated in Columbia, Md. The DOI reading was obtained by using the I2RGlow Box, Model GB11-8 GM, manufactured by Instrument for Research andIndustry, located at Cheltenham, Pa.

Table 1 sets forth the recorded gloss and DOI measurements and providesa comparison of standard paint films with and without a mask, relativeto the paint films of the present invention with and without a gloss andDOI retaining layer. The mask used for the experiments was SoliantPremask commercially available from Soliant, LLC of Lancaster, S.C.

TABLE 1 Before thermoforming After thermoforming 20° Gloss 60° Gloss DOI(%) 20° Gloss 60° Gloss DOI (%) Royal Ruby Red Standard FLUOREX ® Paint63 76 80 21 67 10 Film w/o mask Standard FLUOREX ® Paint 63 76 80 52 7660 Film with mask Paint Film without Gloss and 80 86 80 31 78 10 DOIRetaining Layer Paint Film with Gloss and 74 83 90 68 83 90 DOIRetaining Layer Bright Silver Standard FLUOREX ® Paint 68 90 60 30 79 0Film w/o mask Standard FLUOREX ® Paint 68 90 60 50 87 20 Film with maskPaint Film without Gloss and 84 100 70 34 94 0 DOI Retaining Layer PaintFilm with Gloss 81 100 80 79 100 50 and DOI Retaining Layer TarnishSilver Standard FLUOREX ® Paint 71 89 70 39 82 10 Film w/out maskStandard FLUOREX ® Paint 71 89 70 47 83 20 Film with mask Paint Filmwithout Gloss and 78 89 70 19 66 0 DOI Retaining Layer Paint Film withGloss and 77 95 70 72 95 40 DOI Retaining Layer

The clear coat for the standard FLUOREX® paint film of Table 1 was madewith the following formulation:

ELVACITE 2042 0.11920 g KYNAR 500 0.30650 g DB ACETATE 0.18930 g DMPDIMETHYL PHTHALATE 0.18930 g XYLENE 0.18940 g TINUVIN 900 0.00630 g

The color coat for the standard paint film used the above formulation asa clear base. The clear coat for paint film with and without glossretaining layer used the formulation shown in Clear Coat Composition B.The gloss retaining layer used the formulation shown in Gloss and DOIRetaining Composition D. The clear base used for the color coat for thepaint film with and without gloss retaining layer was the same as theone shown. The color formulations for each of the colors (Ruby Red,Bright Silver and Tarnish Silver) are commercially available fromSoliant, LLC of Lancaster, S.C.

Table 1 demonstrates that the Paint Film with Gloss and DOI Retaininglayer offers an improvement over the paint film with a mask. It issignificant that the paint films with the Gloss and DOI retaining layerare able to get in the lower end of the 20 degree gloss range fortraditional paint, which even paint films with a mask have been unableto achieve. Traditional paints typically have a 70+ number for 20 degreegloss.

It will therefore be readily understood by those persons skilled in theart that the present invention is susceptible of broad utility andapplication. Many embodiments and adaptations of the present inventionother than those herein described, as well as many variations,modifications and equivalent arrangements, will be apparent from orreasonably suggested by the present invention and the foregoingdescription thereof, without departing from the substance or scope ofthe present invention. Accordingly, while the present invention has beendescribed herein in detail in relation to its preferred embodiment, itis to be understood that this disclosure is only illustrative andexemplary of the present invention and is made merely for purposes ofproviding a full and enabling disclosure of the invention. The foregoingdisclosure is not intended or to be construed to limit the presentinvention or otherwise to exclude any such other embodiments,adaptations, variations, modifications and equivalent arrangements.

1. (canceled)
 2. The method according to claim 41, wherein processing isselected from the group consisting of forming or molding.
 3. The methodaccording to claim 2, wherein the forming is thermoforming at athermoforming temperature.
 4. The method according to claim 3, whereinthe gloss and distinctness of image retaining layer has a tensilestrength that is the same as or higher than the higher of the tensilestrength of either the clear coat layer or the color coat layer at thethermoforming temperature.
 5. The method according to claim 4, whereinthe gloss and distinctness of image retaining layer has a tensilestrength that is higher than the higher of the tensile strength ofeither the clear coat layer or the color coat layer at the thermoformingtemperature.
 6. The method according to claim 41, wherein the gloss anddistinctness of image retaining layer is cast or coated.
 7. The methodaccording to claim 41, wherein the gloss and distinctness of imageretaining layer comprises a polymer selected from the group consistingof urethane, acrylic, fluoropolymer, nylon, an alloy thereof, and acombination thereof.
 8. The method according to claim 7, wherein theurethane is a polyurethane.
 9. The method according to claim 7, whereinthe fluoropolymer is polyvinylidene fluoride, polyvinyl fluoride, analloy thereof, or a combination thereof.
 10. The method according toclaim 41, wherein the gloss and distinctness of image retaining layer ispresent between the clear coat layer and the color coat layer of thepaint film.
 11. The method according to claim 41, wherein the paint filmfurther comprises a color adjustment layer.
 12. The method according toclaim 11, wherein the color adjustment layer is present between thegloss and distinctness of image retaining layer and the color coatlayer.
 13. The method according to claim 41, wherein the part is anautomobile part.
 14. The method according to claim 41, wherein the glossand distinctness of image retaining layer is about 0.2 mils to about 2.0mils in thickness.
 15. The method according to claim 41, wherein thegloss and distinctness of image retaining layer further comprises across-linking agent.
 16. The method according to claim 15, wherein thecross-linking agent is selected from the group consisting ofpoly-aziridine, poly-isocyanate, and blocked poly-isocyanate, and aminocross-linking agents.
 17. The method according to claim 15, wherein thecross-linking agent is present in an amount from about 0.1 to about 4.0weight percent.
 18. The method according to claim 41, further comprisinga primer layer.
 19. The method according to claim 41, further comprisingan adhesive layer.
 20. A method of making a decorative paint filmlaminate having high gloss and distinctness of image after processingfor providing a decorative finish for a part, the method comprising:obtaining the paint film comprising: a clear coat layer, a gloss anddistinctness of image retaining layer, and a color coat layer; whereinthe gloss and distinctness of image retaining layer has a tensilestrength the same as or higher than the higher of the tensile strengthof either the clear coat layer or the color coat layer at thethermoforming temperature.
 21. The method according to claim 20, whereinthe tensile strength of the gloss and distinctness of image retaininglayer is higher than the higher of the tensile strength of either theclear coat layer or the color coat layer at the thermoformingtemperature.
 22. A method of making a decorative paint film laminatehaving high gloss and distinctness of image after processing forproviding a decorative finish for a part, the method comprising:obtaining the paint film comprising: obtaining the paint film comprisinga clear coat layer with no mask adhered to the clear coat layer; a glossand distinctness of image retaining layer; and a color coat layer;wherein the gloss and distinctness of image retaining layer comprises apolymer selected from the group consisting of urethane, acrylic,fluoropolymer, nylon, an alloy thereof, and a combination thereof, andwherein the gloss and distinctness of image retaining layer has atensile strength that is the same as or higher than the higher of thetensile strength of either the clear coat layer or the color coat layerat the thermoforming temperature.
 23. A method of making a decorativepaint film laminate having high gloss and distinctness of image afterprocessing for providing a decorative finish for a part, the methodcomprising: obtaining the paint film comprising: obtaining the compositeshaped part comprising a substrate; and a decorative paint film laminatecomprising a paint film comprised of a clear coat layer, a gloss anddistinctness of image retaining layer, and a color coat layer, the paintfilm having an inner surface and an outer surface, a backing sheetapplied to the inner surface of the paint film, and no mask on the outersurface of the paint film, and wherein the gloss and distinctness ofimage retaining layer has a tensile strength that is the same as orhigher than the higher of the tensile strength of either the clear coatlayer or the color coat layer at the thermoforming temperature.
 24. Themethod according to claim 23, wherein the paint film is thermoformableat a thermoforming temperature.
 25. (canceled)
 26. The method accordingto claim 24, wherein the gloss and distinctness of image retaining layerhas a tensile strength that is higher than the higher of the tensilestrength of either the clear coat layer or the color coat layer at thethermoforming temperature.
 27. The method according to claim 23, whereinthe gloss and distinctness of image retaining layer is cast or coated.28. The method according to claim 23, wherein the gloss and distinctnessof image retaining layer comprises a polymer selected from the groupconsisting of urethane, acrylic, fluoropolymer, nylon, an alloy thereof,and a combination thereof.
 29. The method according to claim 28, whereinthe urethane is a polyurethane.
 30. The method according to claim 28,wherein the fluoropolymer is polyvinylidene fluoride, polyvinylfluoride, an alloy thereof, or a combination thereof.
 31. The methodaccording to claim 23, wherein the gloss and distinctness of imageretaining layer is present between the clear coat layer and the colorcoat layer of the paint film.
 32. The method according to claim 23,wherein the paint film further comprises a color adjustment layer. 33.The method according to claim 32, wherein the color adjustment layer ispresent between the gloss and distinctness of image retaining layer andthe color coat layer.
 34. The method according to claim 23, wherein thecomposite shaped part is an automobile part.
 35. The method according toclaim 23, wherein the gloss and distinctness of image retaining layer isabout 0.2 mils to about 2.0 mils in thickness.
 36. The method accordingto claim 23, wherein the gloss and distinctness of image retaining layerfurther comprises a cross-linking agent.
 37. The method according toclaim 36, wherein the cross-linking agent is selected from the groupconsisting of poly-aziridine, poly-isocyanate, blocked isocyanate, andamino cross-linking agents.
 38. The method according to claim 36,wherein the cross-linking agent is present in an amount from about 0.1to about 4.0 weight percent.
 39. The method according to claim 23,further comprising a primer layer.
 40. The method according to claim 23,further comprising an adhesive layer.
 41. A method of making adecorative paint film laminate having high gloss and distinctness ofimage after processing for providing a decorative finish for a part, themethod comprising: obtaining a paint film thermoformable at athermoforming temperature, the paint film having an inner surface and anouter surface, the paint film comprising a clear coat layer as the outersurface, a color coat layer, and a gloss and distinctness of imageretaining layer between the clear coat layer and the color coat layer,the gloss and distinctness of image retaining layer having a tensilestrength the same as or higher than the higher of the tensile strengthof either the clear coat layer or the color layer at the thermoformingtemperature; and applying a backing sheet to the inner surface of thepaint film.
 42. The method of of claim 41, wherein the gloss anddistinctness of image retaining layer has a tensile strength higher thanthe higher of the tensile strength of either the clear coat layer or thecolor coat layer at the thermoforming temperature.